Chemistry of Several Sterically Bulky Molecules with P=P, P=C, and C≡P Bond.

Several sterically protected, low-coordinate organophosphorus compounds with P=P, P=C, and C≡P bond are described in this study. Molecules such as diphosphenes, phosphaalkenes, 1-phosphaallenes, 1,3-diphosphaallenes, 3,4-diphosphinidenecyclobutenes, and phosphaalkynes are stabilized with an extremely bulky 2,4,6-tri-t-butylphenyl (Mes*) group. The synthesis, structures, physical, and chemical properties of these molecules are discussed, together with some successful applications in catalytic organic reactions.

Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu3C6H2P=C: and effects of conjugation between the P=C and aromatic moieties.

The intramolecular C-H insertion of the Mes*-substituted phosphanylidenecarbene [Mes*P=C:] (Mes* = 2,4,6-t-Bu3C6H2) and physicochemical properties of the cyclized product, 6,8-di-tert-butyl-3,4-dihydro-4,4-dimethyl-1-phosphanaphthalene were studied based on ab initio calculations. Whereas the alternative Fritsch-Buttenberg-Wiechell-type rearrangement requires almost no activation energy, the intramolecular cyclization needs an activation energy of 12.3 kcal/mol at the MP2(full)/6-31G(d) condition. DFT calculations supported that the optimized structure of the cyclization product of Mes*P=C: suggests remarkable conjugation effects between the nearly coplanar P=C skeleton and the aryl moiety.

Diverse reactions of sterically-protected 1,3-diphosphacyclobutane-2,4-diyls with hydride.

Hydride-induced elimination of resonance stabilized substituents from a phosphorus center of 1,3-diphosphacyclobutane-2,4-diyls leads to the formation of versatile cyclic phosphaallyl anions that are useful for the construction of various electrophile-modified biradical species.

Modeling the direct activation of dihydrogen by a P2C2 cyclic biradical: formation of a cyclic bis(P-H lambda(5)-phosphorane).

The synthesis of a remarkable cyclic bis(P-H lambda(5)-phosphorane) is reported. A stable phosphorus-heterocyclic biradical, 1,3-diphosphacyclobutane-2,4-diyl, sequentially accepts negatively and positively charged hydrogen atoms to afford 2,4-diphospha-1,3-cyclobutadiene with a diylidic structure containing two P-H bonds.

Synthesis of dihydrothiophene, thiophene, and their selenium analogues carrying four phosphoryl groups.

[reaction: see text] Sodium hydrosulfide undergoes addition to two molecules of bis(diethoxyphosphoryl)acetylene followed by cyclization to give a 2,3-dihydrothiophene carrying four phosphoryl groups. Oxidation of the 2,3-dihydrothiophene with mCPBA gives the corresponding sulfoxide or sulfone depending on the ratio of the reagents, and the sulfoxide is dehydrated to afford a tetraphosphorylthiophene. The corresponding dihydroselenophene and selenophene are also synthesized in a similar manner.

Catalytic applications of transition-metal complexes bearing diphosphinidenecyclobutenes (DPCB).

The preparation and characterization of sterically protected diphosphinidenecyclobutenes bearing two two-coordinate phosphorus atoms are described from the viewpoint of the development of a novel type of bidentate ligand for transition-metal complexes. They form complexes with group 6 metals such as chromium, molybdenum and tungsten, group 8 metals such as ruthenium, group 10 metals such as palladium and platinum, and group 11 metals such as copper and gold. Some of them can be used as catalysts for synthetic reactions such as cross-coupling of the Sonogashira type, Suzuki-Miyaura coupling, Ullmann coupling, Kosugi-Migita-Stille coupling, cyanation, polymerization of ethylene, dehydrogenative hydrosilylation of ketones, hydroamination of 1,3-butadienes, and direct alkylation or amination of allylic alcohols of Tsuji-Trost reactions.

Structural and coordination properties of 1,2-bis(cyclopropyl)-3,4-bis(2,4,6-tri-tert-butylphenyl)-3,4-diphosphinidenecyclobutene prepared by dehydrogenative homocoupling of 3-cyclopropyl-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaallene.

According to a protocol for the synthesis of phosphaallenes we recently established, 3-cyclopropyl-1-(2,4,6-tri-tert-butylphenyl)-1-phosphallene was obtained from (Z)-2-bromo-3-cyclopropyl-1-(2,4,6-tri-tert-butylphenyl)-1-phosphapropene. A novel bidentate ligand, 1,2-bis(cyclopropyl)-3,4-bis(2,4,6-tri-tert-butylphenyl)-3,4-diphosphinidenecyclobutene, was prepared by oxidative homocoupling of 3-cyclopropyl-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaallene in the presence of butyllithium, together with the generation of hydrogen gas. The 1,2-bis(cyclopropyl)-3,4-diphosphinidenecyclobutene was allowed to react with (tht)AuCl (tht = tetrahydrothiophene) to afford the corresponding digold(I) complex of a six-membered metallacycle containing the P=C-C=P skeleton. The molecular structures of the 2-bromo-3-cyclopropyl-1-phosphapropene, 1,2-bis(cyclopropyl)-3,4-diphosphinidenecyclobutene and the digold complex were unambiguously determined by X-ray crystallography and are discussed from the point of view of the cyclopropyl conjugation.

Synthesis and redox properties of crowded triarylphosphines possessing ferrocenyl groups.

Crowded triarylphosphines possessing ferrocenyl groups [(4-ferrocenyl-2,6-diisopropylphenyl)(n)(2,4,6-triisopropylphenyl)(3-n)P (5a, n = 1; 5b, n = 2; 5c, n = 3)] were synthesized by the reaction of the corresponding arylcopper(I) reagents with the diarylchlorophosphines. Structures of the triarylphosphines were studied by 1H, 13C, and 31P NMR spectroscopies, and the characteristic patterns of the proton signals of the 2,6-isopropyl groups and upfielded 31P chemical shifts suggest structural similarities of the triarylphosphine moiety to the previously reported tris(2,4,6-triisopropylphenyl)phosphine (2). X-ray crystallography of 5c also revealed that the structure around the phosphorus is similar to that of 1, where the average bond angle and length around the phosphorus atom are 110.8 degrees and 1.854 A, respectively. According to the electrochemical measurements, phosphines 5a, 5b, and 5c are reversibly oxidized in two, three, and four steps, respectively, which suggests significant electronic interaction among the triarylphosphine and the ferrocene redox centers as well as weak interaction among the ferrocene redox centers. The EPR spectra obtained at cryogenic temperature after oxidation of phosphines 5a, 5b, and 5c are superpositions of those for the cation radicals of the crowded triarylphosphine and ferricinium. The solution spectra obtained at 293 K, which consist of two lines typical of the cation radical of the crowded triarylphosphines, become weaker as the number of the ferrocenyl groups increases and the cation radical of 5c does not show EPR signals. These findings suggest not only instability of the tetra(cation radical) of 5c but also the course of oxidation where the ferrocenyl groups in the periphery of the molecules are oxidized at first.

Coordination behavior of sterically protected phosphaalkenes on the AuCl moiety leading to catalytic 1,6-enyne cycloisomerization.

Mes*-substituted 2,3-dimethyl-1,4-diphosphabuta-1,3-diene, 1,2-diphenyl-3,4-diphosphinidenecyclobutene, 2,2-bis(methylsulfanyl)-1-phosphaethene, and 3,3-diphenyl-1,3-diphosphapropenes (Mes* = 2,4,6-tri-tert-butylphenyl) were employed as P ligands of gold(I) complexes. The (E,E)-2,3-dimethyl-1,4-diphosphabuta-1,3-diene functioned as a P2 ligand for digold(I) complex formation with or without intramolecular Au-Au contact, which depends on the conformation of the 1,3-diphosphabuta-1,3-diene. The 1,2-diphenyl-3,4-diphosphinidenecyclobutene, which has a rigid s-cis P=C-C=P skeleton, afforded the corresponding digold(I) complexes with a slight distortion of the planar diphosphinidenecyclobutene framework and intramolecular Au-Au contact. In the case of the 2,2-bis(methylsulfanyl)-1-phosphaethene, only the phosphorus atom coordinated to gold, and the sulfur atom showed almost no intra- or intermolecular coordination to gold. On the other hand, the 1,3-diphosphapropenes behaved as nonequivalent P2 ligands to afford the corresponding mono- and digold(I) complexes. Some phosphaalkene-gold(I) complexes showed catalytic activity for 1,6-enyne cycloisomerization without cocatalysts such as silver hexafluoroantimonate.

Synthesis of phosphorus ylides bearing a P-H bond from a kinetically stabilized 1,3,6-triphosphafulvene.

In mixing 2,4,6-tris(2,4,6-tri-tert-butylphenyl)-1,3,6-triphosphafulvene with alkyllithium compounds and acetic acid, both of nucleophilic alkylation and electrophilic protonation occurred at the exo sp2-phosphorus atoms to afford [2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclopentadienylidene](alkyl)(2,4,6-tri-tert-butylphenyl)phosphoranes which are phosphorus ylides that bear a P-H bond. A phosphorus ylide bearing both P-H and P-F bonds was obtained by reaction of 2,4,6-tris(2,4,6-tri-tert-butylphenyl)-1,3,6-triphosphafulvene with hydrogen tetrafluoroborate, and the structure was determined by X-ray crystallography. Both P=C double bond and P(+)-C(-) zwitterionic character was indicated by the metric parameters. The isolated phosphorus ylide bearing a P-H bond, [2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclopentadienylidene](2,4,6-tri-tert-butylphenyl)phosphorane, showed no isomerization by H-migration to the corresponding phosphinodiphospholes, probably due to the pi-accepting ability of the unsaturated PC bonds and aromaticity of the C3P2 ring. The ylide structure and aromaticity of 2,4-diphosphacyclopenta-2,4-dienylidenephosphorane was characterized by theoretical calculations. In addition, the regioselective protonation of the lithiated phosphinodiphospholes generated from the 1,3,6-triphosphafulvene is discussed.

Phosphaquinomethane and phosphathienoquinomethanes, and their anion radicals.

Phosphaquinomethane and phosphathienoquinomethanes sterically protected by Mes* (Mes* = 2,4,6-tri-tert-butylphenyl) were synthesized by 1,6-dehydration of the corresponding 4-phosphinoaryl carbinols. Structural similarities to the conventional quinoid compounds were revealed by 1H, 13C, and 31P NMR study and further confirmed by X-ray crystallography of the phosphathienoquinomethane. The corresponding anion radicals were generated by reduction with sodium, and considerable delocalization of an unpaired electron was demonstrated by EPR.

Synthesis, structure, and reactivity of novel 3,4-diphosphacyclobutenes bearing silyl groups.

[reaction: see text] Copper-mediated homocoupling of sterically hindered 2-(2,4,6-tri-tert-butylphenyl)-1-trialkylsilyl-2-phosphaethenyllithiums afforded 1,2-bis(trialkylsilyl)-3,4-diphosphacyclobutenes (1,2-dihydrodiphosphetenes) through a formal electrocyclic [2+2] cyclization in the P=C-C=P skeleton as well as 2-trimethylsilyl-1,4-diphosphabuta-1,3-diene. Reduction of 1,2-bis(trimethylsilyl)-3,4-diphosphacyclobutenes followed by quenching with electrophiles afforded ring-opened products, (E)-1,2-bis(phosphino)-1,2-bis(trimethylsilyl)ethene and (Z)-2,3-bis(trimethylsilyl)-1,4-diphosphabut-1-ene. The structures of the ring-opened products indicated E/Z isomerization around the C=C bond after P-P bond cleavage of 5, and the isomerization of the P-C=C skeleton. Ring opening of 1,2-bis(trimethylsilyl)-3,4-diphosphacyclobutenes affording (E,E)- and (Z,Z)-1,4-diphosphabuta-1,3-dienes was observed upon desilylation.

Solvent free amination reactions of aryl bromides at room temperature catalyzed by a (pi-allyl)palladium complex bearing a diphosphinidenecyclobutene ligand.

An air- and moisture-stable (pi-allyl)palladium complex bearing a unique diphosphinidenecyclobutene ligand effectively catalyzes amination reactions of aryl bromides with amines, where the reactions proceed under mild conditions without solvent, with 2 mol % of catalyst and 1 equiv of t-BuOK at room temperature. Under these conditions the amination products were obtained in good to excellent isolated yields.

Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of aryl halides.

1,2-Diphenyl-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutene was used as an additive ligand in copper-catalysed amination reactions of halobenzenes with amines in the presence of base to afford the corresponding secondary or tertiary amines in good to excellent yields.

Preparation and properties of phosphaethynes bearing bulky aryl groups with electron-donating substituents at the para position.

Phosphaethynes bearing a 2,6-di-tert-butyl-4-(dimethylamino)phenyl, 2,6-di-tert-butyl-4-methoxyphenyl, or 2,6-di-tert-butylphenyl group were prepared. A (31)P NMR spectroscopic investigation of the chemical shifts indicated that electron-donating groups at the para position cause shifts to a higher field. Bathochromic shifts caused by the electron-donating groups were apparently observed in UV-vis spectra. The structure of 2-[2,6-di-tert-butyl-4-(dimethylamino)phenyl]-1-phosphaethyne was analyzed by X-ray crystallography.

Formation and electrochemical properties of a 1,4-diphosphafulvene including formal dimerization of phosphaallene.

Reactions of sterically protected 2-bromo-3-phenyl-1-phosphapropenes with bases such as tert-butyllithium and potassium tert-butoxide successfully afforded a bulky 1,4-diphosphafulvene (Mes = 2,4,6-tBu(3)C(6)H(2)) through a novel and formal dimerization pathway of 1-phosphaallene, together with small amounts of 3-phenyl-1-phosphaallene and 3,4-diphosphanylidenecyclobutene. The structure of the 1,4-diphosphafulvene was confirmed by X-ray crystallography indicating somewhat flattened phosphorus atoms due to the bulky Mes groups. The electrochemical properties of the 1,4-diphosphafulvene were investigated to show promising suitability as an electron donor, and indeed, it afforded a charge-transfer complex with TCNQ. Preparation and structural elucidation of an alkoxy-functionalized 1-phosphaallene was also performed, and the effect of the alkoxy group on the 1-phosphaallene moiety was characterized.

Preparation and reactions of 1,3-diphosphacyclobutane-2,4-diyls that feature an amino substituent and/or a carbonyl group.

The preparation and properties of a 1-amino-1,3-diphosphacyclobutane-2,4-diyl and a 1-benzoyl-1,3-diphosphacyclobutane-2,4-diyl, which can be regarded as functionalized cyclic biradical derivatives, were investigated. Hydrolysis of 1-diisopropylamino-3-methyl-2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl (7), which is formed by reaction of Mes*C[triple chemical bond]P (4; Mes*=2,4,6-tBu(3)C(6)H(2)) with lithium diisopropylamide and iodomethane, resulted in ring-opening of the 1,3-diphosphacyclobutane-2,4-diyl skeleton, as well as de-aromatization of one of the Mes* rings. 3-Oxo-1,3-diphosphapropene 8 and 7-phosphabicyclo[4.2.0]octa-1(8),2,4-triene 9 were the resultant products, and these were subsequently characterized. Isomerization and oxidation of 7 occurred in the presence of TEMPO (2,2,6,6-tetramethyl-1-piperidinoxy) to give the first example of a cyclic dimethylenephosphorane derivative, namely 3-oxo-1,3-diphospha-1,4-diene 10. 1-Benzoyl-3-tert-butyl-2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl (12) was isolated and characterized from the reaction of 4 with tert-butyllithium and benzoyl chloride. Compound 12 was subsequently heated and underwent rearrangement of the benzoyl group and ring-expansion to afford 1-oxo-1H-[1,3]diphosphole 13. Reaction of 4 with lithium diisopropylamide and benzoyl chloride afforded the 2H-[1,2,4]oxadiphosphinine 15, which was probably formed through the 1,3-diphosphacyclobutane-2,4-diyl intermediate 14. Thermolysis of 15 afforded 1-oxo-1H-[1,3]diphosphole 16 in an Arbuzov-type rearrangement.

Preparation and coordination properties including catalytic activities of a bulky 2-methyl-3-thioxo-1,3-diphosphapropene.

[reaction: see text] 2-Methyl-3,3-diphenyl-3-thioxo-1-(2,4,6-tri-tert-butylphenyl)-1,3-diphosphapropene, which bears a P=C-P=S skeleton, was prepared and used as a ligand of transition-metal complexes. The palladium complexes containing the ligated 3-thioxo-1,3-diphophapropene were stable and used for catalytic reactions such as cross-couplings and direct conversion of allyl alcohol to allylaniline.